Dielectric thin films from fluorinated precursors

ABSTRACT

New precursors and processes are disclosed for making fluorinated, low dielectric constant ε thin films that have higher dimensional stability and are more rigid than fluorinated poly (para-xylylenes). The fluorinated, low dielectric constant thin films can be prepared from reactions of an ethylenic-containing precursor with benzocyclobutane-, biphenyl- and/or dieneone-containing precursors. The fluorinated, low dielectric constant thin films are useful for fabrications of future &lt;0.13 μm integrated circuits (ICs). Using fluorinated, low-dielectric constant thin films prepared according to this invention, the integrity of the dielectric, copper (Cu) and barrier metals, such as Ta, can be kept intact; therefore improving the reliability of the IC.

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application is a divisional application of U.S. patentapplication Ser. No. 10/028,198, filed Dec. 20, 2001, which isincorporated herein in its entirety for all purposes.

BACKGROUND

[0002] This invention relates to precursors and methods for making thinfilms that are useful for the fabrication of integrated circuits (“IC”).In particular, this invention relates to thin films that are created bypolymerizing fluorinated ethylinic precursors with fluorinatedbenzocyclobutane precursors, fluorinated biphenyl or fluorinateddieneone precursors. The resultant thin films have increasedcompositional strength, a low-dielectric constant (“ε”), and are stableat high temperatures.

[0003] As integrated circuits (“ICs”) have become progressively moremicrominiaturized to provide higher computing speeds, current dielectricmaterials used in the manufacturing of the ICs have proven to beinadequate in several ways. These materials, for instance, have highdielectric constants, difficulty to use in the manufacturing process,have inadequate thermal instability and generate of toxic by-products.ICs are made by depositing layers of elements and/or compounds on asemiconductor wafer using a variety of techniques that are well known inthe art of fabricating such devices. Specialized material are used toisolate layers on the IC and reduce the charge (i.e. capacitance) thatcan be stored in between conducting elements of the IC. To reduce thepotential capacitance in certain layers, it is preferable that thematerials have a low dielectric constant (“ε”). Low dielectric constantmaterials can be deposited by a variety of methods, including spin-onand chemical vapor deposition (CVD). The composition and characteristicsof the dielectric materials are determined from its precursors as wellas the processes and reactions such precursors undergo while beingintegrated into the IC. As used herein, spin-on refers to the ICmanufacturing process whereby the substrate is rotated about an axisperpendicular to its surface while, or immediately after, a coatingmaterial is applied to the surface. As ICs become smaller and morefunctional, a dielectric material with ε that is 2.7 or lower will berequired.

[0004] Other properties such as thermal stability, compositionalintegrity and process compatibility are important factors that must beconsidered when integrating a dielectric material into an IC. Forexample, a dielectric material should retain its integrity during theprocesses involved in IC fabrication. These processes include reactiveion etching (“RIE”) or plasma patterning, wet chemical cleaning ofphotoresist, physical vapor depositions (“PVD”) of barrier materials andcap layers, electroplating and annealing of copper (“Cu”) andchemical-mechanical polishing (“CMP”) of copper. In addition, thedielectric should have sufficient dimensional stability. Interfacialstresses resulting from a coefficient of thermal expansion (“CTE”)mismatch between the dielectric and barrier material should not inducestructural failure of the barrier material during and after annealing ofcopper. In addition, the interfacial adhesion of dielectric and theother barrier material should be sufficient to overcome interfacial andshear stresses and warrant good adhesion after annealing and CMP ofcopper. Corrosive organic elements used for IC processing can causeinterfacial corrosion of the barrier material, and it is essential thatthe dielectric material does not allow the organic elements to diffuseinto the barrier material layer. In addition, to maintain its electricalintegrity after fabrication of the ICs, the dielectric should be freefrom contamination by the barrier material. Furthermore, the interfacesof dielectric and the barrier material should be free from moisture andno ionic migration occurs when the ICs are operating under electricalbias.

[0005] Dielectric materials that have been traditionally used in ICswere either solid or porous thin films. There are advantages anddisadvantages to each. For example, the advantages of solid dielectricmaterials include: higher dimensional and structural integrity andbetter mechanical strength than porous dielectric materials, but thedisadvantage is higher dielectric constant. In contrast, the advantageof porous dielectric materials is lower dielectric constant due to thepresence of air inside tiny pores of these materials. Current solidmaterials are unable to achieve stability, integrity and strength with adielectric constant below 2.7.

[0006] The “solid” polymer films or “pin-hole free” films contain voidsthat can generally range between 3 to 5 volume % of the films. However,the average void sizes in a cross-section of a well prepared “pin-holefree” or “solid” films are only few Angstroms. It is critical that thepore sizes of the thin films be relatively small in order to be usefulfor fabrication of current or future generation of ICs. For example, thepore sizes should be less than the mean free path (i.e. 50 to 100Angstroms) of the barrier material, which is typically Tantalum (“Ta”).

[0007] The removal of solvents or sacrificing materials can result inadditional porosity and low dielectric constant in “pin-hole free”polymer films. However, when the sacrificing materials have differentcompatibilities with the polymer matrix, the result can lead to polymeraggregation and pore sizes larger than 100 Angstroms. The resulting thinfilm dielectric has poor mechanical properties due to localizeddegradation caused by large pores or their aggregates. The presence ofpores in theses dielectric materials normally results in holes oh newlyformed surfaces, thus making subsequent depositions of a continuous,thin <50-100 Å) barrier layers and copper seed layers very difficult ifnot impossible. Additional problems with traditional porous thin filmsare they often exhibit reliability problems due to the inclusion ofbarrier metal inside the dielectric layer, as occurs after PVD of Ta.Porous dielectric materials are also difficult to integrate into ICfabrications that involve a CMP process. To further complicate theprocess, large surface areas in porous films lead to high wateradsorption that can limit the electrical reliability of the IC.

[0008] Precursors such as Bicyclobutene (“BCB”) can be used to make thinfilms in a copper dual damascene structure without the need for abarrier layer such as Ta, however, the dielectric constant of BCB isgreater than 2.7. Introduction of air bubbles into the BCB during theprocess can increases porosity and a consequential decrease of thedielectric constant. At 20% porosity, BCB has a dielectric constant ofabout 2.3. Unfortunately, the porous BCB and other dielectric materialsthat can achieve a ε≦2.4 are too soft for CMP and not suitable forfabrication of current and future ICs.

[0009] Plasma polymerization of fluorinated precursor molecules has alsobeen described. For example, Kudo et al., Proc. 3d Int. DUMICConference, 85-92 (1997) disclosed polymers made from C₄F₈ and C₂H₂ witha dielectric constant of 2.4. The polymers had a glass transitiontemperature (“Tg”) of 450° C. However, despite its low leakage currentdue to presence of sp³C—F bonds, a low thermal stability occurred due topresence of sp³C—F and sp³C-sp³-C bonds in the films. Thus, thesefluorinated polymers are unable to withstand the prolonged hightemperatures necessary for IC manufacture. In addition, LaBelle et al,Proc, 3d Int. DUMIC Conference, 98-105 (1997) also described the use ofCF₃—CF(O)—CF₂ precursors in a pulsed plasma CVD process, which resultedin some polymer films with a dielectric constant of 1.95. However, inspite of the low dielectric constant, these polymer films also had a lowthermal stability due to presence of sp³C-sp³C and sp³C—F bonds in thesefilms.

[0010] Other fluorinated compounds described by Wary et al,(Semiconductor International, June 1996, 211-216) used the dimerprecursor, (α, α, α¹, α¹), tetrafluoro-di-p-xylylene (i.e.{—CF₂—C₆H₄—CF₂—}₂) and a thermal CVD process to manufacture ParyleneAF-4™, which has the structural formula: {—CF₂—C₆H₄—CF₂—}_(n). Filmsmade from Parylene AF44™ have a dielectric constant of 2.28 and haveincreased thermal stability compared to the above-mentioned dielectricmaterials. Films made of Parylene AF-4™ lost only 0.8% of its weightover a 3-hour period at 450° C. under a nitrogen atmosphere. However,there are disadvantages to the known methods the manufacture of thefluorinated poly (para-xylylenes), or Parylene AF44™. First, themanufacture of their precursors is inefficient because the chemicalreactions have low yields, and the process is expensive and producestoxic byproducts. Further, it is difficult to eliminate redimerizationof the reactive intermediates. When deposited along with polymers, thesedimers decrease the thermal stability and mechanical strength of thefilm.

[0011] In our co-pending applications, we have disclosed somepin-hole-free polymer dielectric that can be prepared from transportpolymerization process. These dielectric materials consist of sp²C—F andhyperconjugated sp³C—F in their polymer chains, thus they have ε≦2.4,and they are thermally stable for fabrication of future ICs. Herein, wedescribe precursors and processes for making thin films from precursorsthat results in polymers with low dielectric constant, improvedcompositional strength and high temperature stability that shouldprovide low cost alternatives for fabrication of miniaturized ICs.

SUMMARY

[0012] The present invention includes the polymerization of precursorsfor production of a dielectric thin film with physical properties thatovercome the disadvantages of prior art. In particular, this inventionrelates to thin films that are created by polymerizing fluorinatedethylinic precursors with fluorinated benzocyclobutane, fluorinatedbiphenyl or fluorinated dieneone precursors. The resultant thin filmshave increased dimensional stability, a low-dielectric constant (“ε”),and are stable at high temperatures. The thin films described herein canbe incorporated into the manufacturing process of integrated circuits,active matrix liquid crystal display or fiber optic devices. In additionto the disclosure of the precursors for the dielectric thin films, aspin-on method for producing dielectric thin films in the manufacturingprocess is also discussed. Other objects, aspects and advantages of theinvention can be ascertained from the review of the detailed disclosure,of the examples, the figures and the claims.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0013] This invention discloses thin fluorinated films with lowdielectric constants (“ε”) that are useful in the manufacture ofintegrated circuits and other electronic devices. Manufacture of smallerand faster integrated circuits requires inter-metal dielectric (IMD) andinter-level dielectric (ILD) materials that minimize the communicationof electrical signals between adjacent conductive lines, referred to asthe interconnects. Low dielectric constant materials are useful tominimize “crosstalk” within and between layers of integrated circuits inaddition to serve many other purposes.

[0014] The polymers prepared from the precursors of the presentinvention contain a high degree of substitution of hydrogen atoms byfluorine atoms. In these polymers, the fluorine in the aromatic ringprovides the low dielectric constant below about 2.6 and molecularrigidity. This rigidity is reflected by high glass transitiontemperature (Tg), high elastic modulus (E) and high shear modulus (G).Their elastic modulus is above about 2.5, and mostly is above 3.5 GPa.

[0015] Films made from Parylene AF44™ have a dielectric constant of 2.28and have increased thermal stability compared many different dielectricmaterials. However, there are disadvantages to the known methods themanufacture of Parylene AF44™. Despite these disadvantages, it isimportant to understand the advantages of such polymer in order toproduce the next generations of thin films. Although not wanting to bebound by theory, the thermal stability of the Parylene AF44™ is due tothe higher bonding energies of the sp²C=sp²C, sp²C—H and sp²C-sp³C bondsof 145, 111 and 102 kcal/mol respectively. In addition, the sp³C—F bondsmay also be involved in hyperconjugation with sp²C=sp²C double bonds ofthe adjacent phenylene groups in Parylene AF44™. This hyperconjugationrenders a higher bond energy for the sp³C—F bonds than are found innon-hyperconjugated sp³C—F bonds.

[0016] Thus, polymers consist of sp²C=sp²C, sp²C—F and hyperconjugatedsp³C—F bonds confer advantages, whereas other types of bonds (such assp³C—F and sp³C—H bonds) do not confer these advantages. The sp²C=sp²Cand other sp²C bonds increase the mechanical strength and increase Td(Decomposition Temperature) of the polymers. The fluorine atoms on thearomatic moieties of the polymers of this invention decrease thedielectric constant and the sp²C—F and hyperconjugated sp³C—F bondsconfer greater thermal stability to these polymers. In contrast,polymers that do not contain these types of bonds have lower thermalstability and higher dielectric constant.

[0017] One embodiment of the present invention pertains to fluorinatedprecursors and processes for making thin polymer films that havelow-dielectric constant and have improved dimensional stability, and arestable at high temperatures. In particular, this invention relates tonovel fluorinated precursors and the methods to process thesefluorinated precursors. These polymers have a dielectric constant εequal to or less than 2.7, thus are useful in the fabrications of ICs.The present invention preferably uses the spin on method to dispense thefluorinated precursors onto the wafer.

[0018] Broadly, one aspect of the present invention pertains to a thinfilm with a low dielectric constant by co-polymerization of anethylenic-containing precursor (Ia) with a benzocyclobutane (IIa′)-, abiphenyl (IIb′)- or a dieneone (IIc′)-containing precursor, or theiradmixture. The ethylenic-containing precursor (Ia) can have thefollowing general structure:

P-(-Z-W)_(n°)  (Ia)

[0019] wherein, W is —H, —F or fluorinated phenyl; n° is an integer of2, and Z is a moiety containing an ethylenic (C≡C) group.

[0020] P can be —C₆H_(4-n)F_(n)-(n=0 to 4);—C₆H_(4-n)F_(n)—CF₂—C₆H_(4-n)F-(n=0 to 4); —C₁₀H_(6-n)F_(n)-(n=0 to 6),or —C₁₂H_(8-n)F_(n)-(n=0 to 8).

[0021] The benzocyclobutane-containing precursor can have the followinggeneral structure (IIa′):

[0022] wherein W′, W″, W′″, W″″, W′″″, and W″″″ are independently thesame or different and are fluorinate phenyl, —F or —H, n′ is an integerof 2. P′ can be —C₆H_(4-n)F_(n)-(n=0 to 4);—C₆H_(4-n)F_(n)—CF₂—C₆H_(4-n)F_(n)-(n=0 to 4); —C₁₀H_(6-n)F_(n)-(n=0 to6), or —C₁₂H_(8-n)F_(n)-(n=0 to 8).

[0023] The diphenyl containing precursors can have the following generalstructures (IIb′):

[0024] wherein each W is fluorinate phenyl, —F or —H, n′ is an integerof at least 2 to a number that is less than total sp²C substitutions onP′. P′ can be —C₆H_(4-n)F_(n)-(n=0 to 4);—C₆H_(4-n)F_(n)—CF₂—C₆H_(4-n)F_(n)-(n=0 to 8); —C₁₀H_(6-n)F_(n)-(n=0 to6), or —C₁₂H_(8-n)F_(n)-(n=0 to 8).

[0025] The dieoneone-containing precursors can have the followinggeneral structures (IIc′):

[0026] wherein each W is fluorinate phenyl, —F or —H, n′″ is an integerof at least 2 to a number that is less than total sp²C substitutions onP′. P′ can be —C₆H_(4-n)F_(n)-(n=0 to 4);—C₆H_(4-n)F_(n)—CF₂—C₆H_(4-n)F_(n)-(n=0 to 8); —C₁₀H_(6-n)F_(n)-(n=0 to6), or —C₁₂H_(8-n)F_(n)-(n=0 to 8).

[0027] Pinhole-free thin films can be prepared by the following steps:

[0028] Precursor molecules, such as ethylenic (Ia) with benzocyclobutane(IIa′), biphenyl (IIb′), or dieneone (IIc′), or their mixture are firstdissolved or suspended in an appropriate solvent. This mixture orsuspension is then dispensed onto the surface of interest by the spin-ontechnique, which results in a thin wet film. The thin wet film is thenheated at 3 to 5° C. per minute to a predefined maximum temperature,T_(max). Thus, the wet film is heated from 5 to 50° C. below the boilingpoint of the solvent. The resultant film is then heated at 10° C. perminute to a maximum temperature, T_(max) that ranges from 10 to 20°below the glass transition temperature (“Tg”) of the thin film. A thinfilm according to this invention has a dielectric constant of less than2.6, preferably less than 2.4. Thus, thin film derived frompolymerization of precursors (IIa′, IIb′ or/and IIc′) with precursor(Ia) are useful for the manufacture of ICs, active matrix LCDs or afiber optic device. In addition, this invention will provide thin filmsthat are compatible with the Dual Damascene process used inmanufacturing of future ICs.

[0029] The heating and curing processes described in the above shouldpreferably conducted under non-oxidative, inert conditions to preventoxidation of prepolymers. Ideally, the processes should be conductedunder nitrogen or vacuum condition on hot plate and inside an oven. Thefinal heating or curing process should be at least 5 to 10 minutes ifconducted on a hot plate, and should be at least 20 to 30 minutes ifconducted inside an oven. The final cure temperature should be at leastreaching to 5 to 10° C. below its maximum achievable Tg, Tg(max). From apractical point of view, Tg(max) is defined here for the Tg that can beobtained by heating the dielectric inside a sample cell in DSC(Differential Scanning Calorimeter) to 450° C. at 10° C. per minuteheating rate under nitrogen atmosphere. The Tg(max) can be obtained byre-scanning the dielectric material inside the sample cell under thesame conditions.

[0030] Set forth in the following illustrations are polymerizationreactions useful to create the low ε thin films from the aboveprecursors (Ia with IIa′, IIb′ and IIc′) of this invention:

[0031] wherein, n″″ is an integer of at least 10, preferably 20.

[0032] P and P′ can be the same for each of the above reactions. P andP′ is independently an aromatic moiety, preferably a fluorinatedaromatic moiety, containing compound. The aromatic moiety includes, butis not limited to:

[0033] —C₆H_(4-n)F_(n)-(n=0 to 4), such as —C₆H₄— and —C₆F₄—;—C₆H_(4-n)F_(n)—CF₂—C₆H_(4-n)F_(n)-(n=0 to 4); napthyenyl moiety,—C₁₀H_(6-n)F_(n)-(n=0 to 6), such as —C₁₀H₆— and —C₁₀F₆—; di-phenylmoiety, —C₁₂H_(8-n)F_(n)-(n=0 to 8), such as —C₆H₂F₂—C₆H₂F₂— and—C₆F₄—C₆H₄—; anthracenyl moiety, —C₁₂H_(8-n)F_(n)—; phenanthrenylmoiety, —C₁₄H_(8-n)F_(n)—; pyrenyl moiety, —C₁₆H_(8-n)F_(n)— and morecomplex combinations of the phenyl and naphthenyl moieties,—C₁₆H_(10-n)F_(n)—. The aromatic moieties could include isomers ofvarious F substitutions and reaction groups (X,Y,Ar′ & D).

[0034] Thus, P and P′ can be an aromatic moiety-containing compounds ofthe following general structures:

[0035] —Ar-L-AR′-, wherein Ar and Ar′ is selected from P or P′. L is alinkage unit such as —O—CH₂—O—, —O—CF₂—O—, —Si(R)₂—O—Si(R)₂, —O—, —CO—,—SO₂—, or —O—Ar—O— groups, and is preferably a —CF₂— group. R can be anaromatic radical, an alkyl radical, —CH₃, or preferably a —CF₃.

[0036] Compounds P and P′, by definition, can be simple organiccompounds, oligomers or polymers. An oligomer is a molecule consistingof many (2 to 10) repeating units in its backbone structure whereas apolymer is a macromolecule consisting of more than 10 to 20 repeatingunits in its backbone structure.

[0037] X in the above compound (I) is an acetylenyl radical, such as—C≡C—W, wherein W is a fluorinate phenyl, —H or —F. (Note that in (Ia),-Z-W equals to-X and n=2 in (I)).

[0038] Y in the above compound (IIa) is a benzocyclobutane radical ofthe following structure (IV):

[0039] wherein each W is a fluorinate phenyl, —F or —H.

[0040] Ar′ in (IIb) is a biphenyl radical of the following structure(V):

[0041] wherein each W is a fluorinate phenyl, —H or —F.

[0042] D in the above compound (IIC) is a dieneone radical of thefollowing structure

[0043] wherein each W is a fluorinate phenyl, —H or —F.

[0044] According to the above reactions, Z is the repeating chemicalstructure of the following structure (VII) for the reaction (1):

[0045] Z′ is (VIII) for the reaction (2):

[0046] Z″ is (IX) for the reaction (3).

[0047] The disclosed invention also includes precursors (Ia′, IIa′, IIb′and IIc′) consisting of more than two functional groups (X, Y, Ar′ and Din I, IIa, IIb and IIc; when n°, n′, n″, or n′″ is greater than 2). Whenprecursors consisting of more than two functional groups are used inpreparations of thin films, it is desirable to balance the total numberof functional groups in (Ia, n°>2) with that of (IIa′, IIb′ or IIc′; n′,n″, or n′″ is greater than 2). Although not wanting to be bound bytheory, the ratio of the total number of functional groups in (Ia) tothat in (II) should be in the range from 0.85 to 1.20, preferablybetween 0.9 to 1.1. In these cases, better cross-linked polymer thinfilms will result.

[0048] In order to achieve a dielectric constant of 2.7 or lower, theabove referenced precursors should consist of a sufficient amount of Fsubstitution to H in their sp²C—H and sp³C—H bonds. Further, in order toachieve thermal stability and higher rigidity, the above referencedprecursors should consist of a substantial amount of F substitution to Hin their sp³C—H bonds. In general, all sp³C—H should be replaced with Fin order to achieve the thermal stability required in IC fabrication.The immediately foregoing does not apply to precursors that include asp³C_(α)—H bond, wherein C_(α) is an alpha carbon connecting to anaromatic group. According to hyper-conjugation principle, the sp³C_(α)—Hbond is substantially more thermally stable than that of a sp³C—H bond.However, to achieve a dielectric constant ε<2.4, the total amount of Fsubstitution to H can be estimated as follows.

[0049] It is known that without any F substitution to H for the aboveprecursors (Ia) and (IIa′, IIb′ and IIc′), the resulting dielectric willhave a constant ε of about 2.65 to 2.75. However, when each C—H bond isreplaced with C—F bond, the constant ε of the resulting polymer will belowered at 0.05 to 0.07 per substitution with a limiting lowest ε ofabout 1.9. Therefore, the ratio of(sp²C—F+sp³C—F)/(sp²C—F+sp³C—F+sp²C—H+sp³C—H) of resulting thin filmsshould be at least 0.4, preferably 0.7.

[0050] To make thin films from the above referenced precursors (I andIIa, IIb and IIc), in general, such precursors are spin coated onto thewafer. The wet film is then conditioned under slow heating rates (3 to5° C./minute) to remove most (80 to 90%) of the solvent(s). Theresulting dry films are then exposed to polymerization conditions thatnormally have various time-temperature-heating rate schedules.

[0051] Under proper processing conditions, solid, “pinhole-free” thinfilms useful for fabrication of ICs can be obtained for polymers (IIIaand IIIb). To obtain “pinhole-free” thin films, solvent-dryingtemperatures are generally need to be at least 20 to 50° C. below theboiling temperature of the solvent. In addition, it is desirable to heatthe wet film under an inert gas such as nitrogen. Polymerization canthen be carried out by heating the resulting wet films slowly from(Tb-20 to 50) to (Tg-T) ° C. Wherein, Tg is the attainable glasstransition temperature for a given polymer and T ranges from 20 to 50°C. Preferably, (Tg-T) preferably should not exceed 450° C. When (Tg-T)approaches 400 to 450° C., the heating time should be less than 30 to 60minutes under such temperatures. During polymerization, the heating ratenormally ranges from 20 to 30° C./minute depending on the thickness ofthe films. For making thin films (<1-2 μm), heating rate can be as highas 40 to 50° C./minute.

[0052] A more restrictive and controlled drying and cure procedure isnecessary to obtain “pinhole-free” thin films for polymer IIIc. Due tothe generation of carbon monoxide during polymerization, thin films ofvarious porosity and pore sizes may result. For example, as notedherein, if the polymerization is carried out for a very dry film under aslow heating rate (5 to 10° C./minute), “pinhole free” thin film can beobtained. However, if polymerization reactions are carried out attemperatures that are higher than the soft temperatures of polymerchains inside the wet films, thin films with porosity will result.Therefore, in principle, thin films with various porosity and pore sizescan be obtained by manipulating the polymerization conditions or weight% of a solvent in a given film. Generally, pore size distribution isuniform, since it is controlled from polymerization reactions that onlyoccur at chain ends. This is different from other conventional methodsthat used co-solvents or low thermally stable inclusions (or sacrificingmaterials) to generate porous dielectrics.

[0053] The invention includes novel precursors containing a fluorinatedaromatic moiety. The precursors are suitable for making thin films withlow dielectric constants and high thermal stability. Additionally, theinvention includes methods for applying thin films of this invention forvarious electronic devices. Therefore, integrated circuits, liquidcrystal displays or fiber optic devices consist of these thin filmsshould have improved electrical and mechanical performances.

[0054] It should be appreciated by those of ordinary skill in the artthat other embodiments may incorporate the concepts, methods,precursors, polymers, films, and devices of the above description andexamples. The description and examples contained herein are not intendedto limit the scope of the invention, but are included for illustrationpurposes only. It is to be understood that other embodiments of theinvention can be developed and fall within the spirit and scope of theinvention and claims.

We claim:
 1. A dielectric thin film prepared by polymerizing anethylenic-containing precursor with a biphenyl-containing precursor. 2.The dielectric thin film of claim 1, wherein the ethylenic-containingprecursor has a general structure of: P-(-Z-W)_(n°)  (Ia); wherein W ishydrogen, fluorine or a fluorinated phenyl; P is an aromatic-moiety witha general structure of —C₆H_(4-n)F_(n)-(n=0 to 4);—C₆H_(4-n)F_(n)—CF₂—C₆H_(4-n)F_(n)-(n=0 to 8); —C₁₀H_(6-n)F_(n)-(n=0 to6), or —C₁₂H_(8-n)F_(n)-(n=0 to 8); Z is a moiety having an ethylenicgroup; and n° is an integer of at least 2, but is less than total sp²Csubstitutions on the P aromatic-moiety.
 3. The dielectric thin film ofclaim 1, wherein the biphenyl containing precursor has a generalstructure of:

wherein W is hydrogen, fluorine or a fluorinated phenyl; P′ is anaromatic-moiety with a general structure of —C₆H_(4-n)F_(n)-(n=0 to 4);—C₆H_(4-n)F_(n)—CF₂—C₆H_(4-n)F_(n)-(n=0 to 8); —C₁₀H_(6-n)F_(n)-(n=0 to6), or —C₁₂H_(8-n)F_(n)-(n=0 to 8); and n″ is an integer of at least 2,but is less than total sp²C substitutions on the P′ aromatic-moiety. 4.The dielectric thin film of claim 1, wherein the dielectric thin filmhas a dielectric constant (ε) value equal to or less than 2.6.
 5. Thedielectric thin film of claim 1, wherein one or more layers of the thinfilm is deposited on an integrated circuit (“IC”) or an electronicdevice.
 6. The dielectric thin film of claim 5, wherein the electronicdevice comprises an active matrix liquid crystal display, or a fiberoptic device.
 7. The dielectric thin film of claim 5, wherein the IC ismanufactured via a dual damascene process comprising the dielectric thinfilm.
 8. A dielectric thin film prepared by polymerizing anethylenic-containing precursor with a dieneone-containing precursor. 9.The dielectric thin film of claim 8, wherein the ethylenic-containingprecursor has a general structure of: P-(-Z-W)_(n°)  (Ia); wherein W ishydrogen, fluorine or a fluorinated phenyl; P is an aromatic-moiety witha general structure of —C₆H_(4-n)F_(n)-(n=0 to 4);—C₆H_(4-n)F_(n)—CF₂—C₆H_(4-n)F_(n)-(n=0 to 8); —C₁₀H_(6-n)F_(n)-(n=0 to6), or —C₁₂H_(8-n)F_(n)-(n=0 to 8); Z is a moiety having an ethylenicgroup; and n° is an integer of at least 2, but is less than total sp²Csubstitutions on the P aromatic-moiety.
 10. The dielectric thin film ofclaim 8, wherein the dieneone-containing precursor has a generalstructure of:

wherein W is hydrogen, fluorine or a fluorinated phenyl; P′ is anaromatic-moiety with a general structure of —C₆H_(4-n)F_(n)-(n=0 to 4);—C₆H_(4-n)F_(n)—CF₂—C₆H_(4-n)F_(n)-(n=0 to 8); —C₁₀H_(6-n)F_(n)-(n=0 to6), or —C₁₂H_(8-n)F_(n)-(n=0 to 8); and n′″ is an integer of at least 2,but is less than total sp²C substitutions on the P′ aromatic-moiety. 11.The dielectric thin film of claim 8, wherein the dielectric thin filmhas a dielectric constant (ε) value equal to or less than 2.6.
 12. Thedielectric thin film of claim 8, wherein one or more layers of the thinfilm is deposited on an integrated circuit (“IC”) or an electronicdevice.
 13. The dielectric thin film of claim 12, wherein the electronicdevice comprises an active matrix liquid crystal display or a fiberoptic device.
 14. The dielectric thin film of claim 12, wherein the ICis manufactured via a dual damascene process comprising the dielectricthin film.
 15. A method of making a dielectric thin film material,comprising: (a) dissolving or suspending the precursors in a solvent togive a solution or suspension of the precursor in the solvent; (b)spinning the solution or the suspension of the precursors in the solventonto a substrate to form a thin wet film; (c) heating the thin wet filmto a temperature that is below a boiling-temperature of the solvent toremove most of the solvent from the thin wet film to form a thin driedfilm; and (d) heating the thin dried film to a temperature that is belowa glass-transition temperature of the thin dried film to give thedielectric thin film material.
 16. The method of claim 15, wherein arate of heating the wet film occurs at 3 to 5° C. per minute to amaximum temperature that is below the boiling-temperature of thesolvent.
 17. The method of claim 16, wherein the wet thin film is heatedto a maximum temperature that ranges from 5 to 50° C. below theboiling-temperature of the solvent.
 18. The method of claim 15, whereina rate of heating the thin dried film occurs at 10° C. per minute to amaximum temperature that is below the glass-transition temperature ofthe thin dried film.
 19. The method of claim 18, wherein the thin driedfilm is heated to a maximum temperature that ranges from 10 to 20° C.below the glass-transition temperature of the thin dried film.